Decoloration of human hair with bleaching compositions containing n-methylol compounds

ABSTRACT

A COMPOSITION FOR BLEACHING KERATINIC FIBERS INCLUDES A MIXTURE OF AN OXIDIZING AGENT AND AT LEAST ONE NMETHYLOL COMPOUND WHICH IS METHYLATED ON THE NITROGEN OF A   -C(=S)-N&lt;   GROUP OR A DERIVATIVE THEREOF. THE OXIDIZING AGENT IS MIXED WITH THE N-METHYLOL COMPOUND OR ITS DERIVATIVE JUST BEFORE APPLICATION OF THE RESULTING MIXTURE TO THE KERATINIC FIBERS.

United States Patent 3,726,638 DECOLORATION OF HUMAN HAIR WITH BLEACHING COMPOSITIONS CONTAIN- ING N-METHYLOL COMPOUNDS Giuliana Ghilardi, Gregoire Kalopissis, and Henri Philippe de Beaulieu, Paris, and Jean-Louis Abegg, Le Perreux, France, assignors to Societe Anonyme dite: LOreal, Paris, France No Drawing. Filed July 9, 1970, Ser. No. 53,674 Int. Cl. D061 3/02; A61k 7/12 U.S. Cl. 8111 6 Claims ABSTRACT OF THE DISCLOSURE A composition for bleaching keratinic fibers includes a mixture of an oxidizing agent and at least one N- methylol compound which is methylated on the nitrogen of a group or a derivative thereof. The oxidizing agent is mixed with the N-methylol compound or its derivative just before application of the resulting mixture to the keratinic fibers.

This invention relates to a novel composition for the hot decoloration of human keratinic fibers.

Heretofore, the use of oxidizing compositions for decoloration of the hair have been known and such compositions employed, as the oxidizing agent, such materials as per salts, and peroxides including hydrogen peroxide. Such compositions were generally in the form of a cream or gel. These known compositions were usually applied to the fibers that were to be bleached for a suflicient period of time, generally in the order of several minutes.

It has now been found, however, that this decoloration or bleaching operation can be improved by causing an essentially spontaneous elevation of the temperature of the decoloration or bleaching composition during use, which elevation of temperature accelerates the decoloration effect produced.

Moreover, the decoloration composition of the present invention also provides strengthening of the hair which, as is known, generally becomes rather pronouncedly degraded by the action of the conventional oxidizing agents.

Moreover, as one embodiment of the present invention, the novel compositions offer the special characteristic of releasing a certain amount of nascent sulfur which improves the ultimate appearance of the hair by eliminating or substantially reducing an undesirable oily or greasy appearance or condition of the hair.

Thus, the compositions of the present invention can provide simultaneous acceleration of the bleaching action, restoration or strengthening of the hair which has undergone degradation in the oxidation reaction to decolor or bleach the same, or which has been degraded by prior treatment, and in certain instances an elimination or substantial reduction of a greasy appearance or condition of the hair.

The novel composition of this invention comprises a mixture of an oxidizing agent and at least one N-methylol compound, the methylol being on the nitrogen of a group, or a derivative of such a compound. The N- methylol compound is admixed with the oxidizing agent immediately before its use.

N-methylol compounds or the derivatives thereof, use- 3,726,638 Patented Apr. 10, 1973 fully employed in this invention have the following formula:

wherein R represents a member selected from the group consisting of hydrogen and alkyl having 1 to 5 carbon atoms and r and r each independently represent a member selected from the group consisting of lower alkyl having 1 to 5 carbon atoms or together with the nitrogen atom to which they are attached form a cyclic ring, optionally containing a hetero atom; R is selected from the group consisting of alkyl having 1 to 5 carbon atoms and CH R wherein R has the same meaning given above.

Representative N-methylol compounds and their derivatives which correspond to the above formula include:

monomethylol thiourea H 0 CHzNH-(fi-NH:

dimethylol thiourea HO CH:-NHC--NHCH2OH monomethylolethylene thiourea CHQOH Hz-Nfi dimethylolethylene thiourea CHZOH CHa-N CHz-N C H: O H

dimorpholinomethyl thiourea monomorpholinomethyl thioureaand dimorpholinomethylethylene thiourea- HzN E) These N-methylol compounds may be readily prepared by known processes by the action of Formol on the respective corresponding thioamides.

Representative derivatives of these N-methylol compounds that can be employed in accordance with the present invention are those that are obtained by etherizing the methylol function, or those obtained by a Mannich reaction, i.e. by conjugated action of Formol and a secondary amine on a thioamide.

The oxidizing agent employed in the compositions of the present invention can be, for example, hydrogen peroxide or a mixture of hydrogen peroxide with a per salt such as sodium percarbonate, potassium percarbonate, sodium persulfate and potassium persulfate or a mixture of hydrogen peroxide with an organic peroxide such as urea peroxide.

Generally the hydrogen peroxide will be employed as an aqueous solution containing about 3-9% H 0 and will be present in the composition in the aqueous form in amounts ranging from about 15-995 weight percent of the total composition. When employed, the per salt can be present in amounts ranging from about 5-10 Weight percent of the total composition. On a H O -water-free basis, the H 0 can be present in amounts ranging from about 9-90%, while on the same basis the per salt can be present in amounts ranging from about 30-40% weight percent of said composition.

The amount of N-methylol compound or the derivative thereof used in combination with the oxidizing agent at the time of use to form the composition of the present invention can depend on such easily ascertainable factors as the particular choice of oxidizing agent employed in the composition as well as on the specific effect that is desired. In general, the amount of N-methylol compound employed is less than the stoichiometric amount relative to the oxidizing agent, but this is not mandatory, especially in the case where the composition is applied very rapidly after mixing. For example, the proportion of N- methylol compound or derivative can range from 0.5 to 1.4 times the stoichiometric proportion of oxidizing agent. Expressed in other terms, the N-methylol compound or its derivative can be present in amounts ranging from about 0.15-7 weight percent based on the total weight of the composition on an aqueous form H 0 basis. On an aqueous free H 0 basis, the amount of N-methylol compound or derivative can be present in amounts ranging from about 0.1-60 weight percent.

In another embodiment of the present invention the novel compositions can also contain hair dyes which permit shading or coloring of the hair at the same time it is bleached. This operation is conventionally termed bleachdyeing or lightening-tinting.

Among the dyes that can be used in the compositions of the invention, are dispersed azo dyes, either complex or soluble, or nitrated dyes such as nitroparaphenylene diamine. With regard to the representative dyes given below, for each dye reference is made, in parenthesis, to the Color Index, 22d ed., 1956, vol. 4, or the 11963 Supplement.

Representative dispersed azo dyes include the dyes sold under the trademark Cibacete (1963 Supplement, pp. 7854 6) y C ba, the tradema k. Asetoquinon p. 4103) by Francolor, the trademark Celliton (vol. 4, pp. 4181-4183) by Basf, and the trademark Artisil (vol. 4, pp. 4136-4137) by Sandoz. Reactant azo dyes can also be used, such as those sold under the trademark Cibacron 1963 Supplement, p. 786) by Ciba, the trademark Reactone (1963 Supplement, p. 786) by Geigy and the trademark Remazol (vol. 4, p. 4416) by Hoechst.

Representative azo dyes with metallic complex that can be used in the compositions of the invention include dyes sold under the trademarks Cibalan (1963 Supplement, pp. 786-787) and Neolan (1963 Supplement, pp. 967- 968) by Ciba, the trademark Irgalan (1963 Supplement, p. 194) by Geigy, the trademarks Vialon-Fast (1963 Supplement, p. 1108) and Palatine-Fast (1963 Supplement, p. 992) by Bast, the trademark Inoderme (1963 Supplement, p. 912-913) by Francolor, and the trademark Lanazyn (1963 Supplement, p. 930) by Sandoz.

The presence of the N-methylol compound or derivative thereof in the oxidizing agent containing composition of this invention makes it possible to obtain a sub stantial elevation of the temperature thereof which activates the bleaching operation. Further, at this elevated temperature a release of nacent sulfur is possible which improves the appearance of the hair by substantially reducing any oily or greasy characteristics of the hair. Further, at these elevated temperatures, a polyaddition or polycondensation reaction can take place which effects a reinforcement of the keratinic fibers.

The pH of the compositions of the present invention is selected as a function of the desired result insofar as bleaching action is concerned. In practice it is that of conventional bleaching agent, i.e. about 3.0-10.5. In this regard, it is known that in the case of weak bleaches, i.e. decolorants that are intended solely to lighten the hair slightly, the pH of these compositions at the end of the decoloration operation has an acid value. In such a situation, the methylol derivatives present in the composition give rise to polycondensation and polyaddition reactions that effect a strengthening of the keratinic fiber.

On the other hand, it is known that decolorant compositions which efrect medium or strong bleaching effects, i.e. a substantial reduction of the hair coloring, have an initial and final basic pH. In such a situation, the methylol derivative present cannot cause polycondensation or polyaddition reactions. To obtain such a polyaddition or polycondensation reation, a rinse with an acid solution at the end of the decoloration process is employed. A lactic acid solution with a pH of 4, for example, is employed as the acid rinse medium. A reaction of the methylol compound or derivative then occurs which permits the attainment (35) improved hair quality and restoration of the keratinic ers.

Other acid rinse media include aqueous acetic acid or formic acid solutions.

The compositions of the present invention contain proportions of oxidant compounds that correspond to those of ordinary decolorant compositions. For example, the compositions of this invention can contain from 50 to 75%, preferably 50 to 66% hydrogen peroxide (6%) and from 30 to per salts.

The compositions of the invention can be provided in various commercial forms, for instance as a lotion or, preferably, a cream or gel. The latter are generally employed since they are easy to use because their viscosity is high and they do not tend to run, but remain in the place where their action is required.

The present invention also relates to a two package composition, one package containing the said methylol compound or derivative and the second package containing the oxidizing agent, the contents of said packages being mixed at the time of use to form the composition of this invention.

The present invention also relates to a process for the decoloration of keratinic fibers, especially human hair, which comprises admixing with an oxidizing agent customarily used for bleaching the hair, at least one N-methylol compound, methylated on the nitrogen of a ll s group or a derivative thereof, impregnating the keratiuic fibers with the resulting composition, permitting said composition to remain in contact with the hair for 15 to 60 minutes and thereafter washing the thus treated fibers.

As a modification of this process wherein moderate or strong bleaching of the hair is effected, alone or simultaneously with tinting or dyeing of the hair, the hair, after washing, is rinsed with an aqueous acidic rinsing medium to restore the fibers of polyaddition or polycondensation of the methylol compound.

According to the invention, a substantial increase in temperature can be attained and the degree or amount of temperature increase depends on the amount of the composition utilized, as well as on the particular methylol and oxidizing agent chosen and the amounts thereof used in the compositions of this invention. A temperature of 30 to 60 C., or even more if desired, can easily be attained with the compositions of this invention.

The following examples are given to illustrate the present invention:

EXAMPLE 1 A weak bleaching composition is prepared by adding at the time of its use 3.8 g. dimethylol thiourea to 100 g. of 10 vol.-3% H solution. The pH of the resulting bleaching composition is 3.5. This mixture is then applied to hair which is light chestnut in color, and the composition is allowed to remain in contact therewith for about 15 minutes. After 5 to 7 minutes, the temperature observed is 50 to 52 C. The thus treated hair is rinse'd after the I minute contact period and is set as usual.

There is a distinct lightening of the hair, by 1 to 1 /2 tones and the hair is lively and brilliant.

EXAMPLE 2 Using essentially the same composition in Example 1 except that the dimethylol thiourea is replaced by 2.7 g. monomethylol thiourea and the pH of the resulting composition is 3.8, the composition is applied to hair having essentially the same initial color as in Example 1.

After application of this composition to the hair and treatment as in Example 1, a lightening of 1 tone to 1 /2 tones is also attained. The hair is lively and brilliant and the hair set holds very well.

EXAMPLE 3 A Weak bleaching composition is prepared by adding, at the time of use, 3.5 g. dimethylolethylene thiourea to 100 g. hydrogen peroxide (6% H 0 volumes. The pH of the solution is 3.

The resulting mixture is then applied to the hair, which has a light chestnut color, and the temperature rises to 50-52" C. in the course of 5 to 7 minutes.

The composition is allowed to act for 15 minutes. Thereafter, the hair is set in the usual manner. A lighteningof the hair by 1 tone to 1 /2 tones is obtained, and the set holds well, the hair being characterized as lively.

EXAMPLE 4 To obtain a tinting-decoloration and a strengthening of light chestnut hair, the following composition is prepared. At the time of use 2.7 g. monomethylol thiourea and 0.1 g. nitro-p-phenylene diamine are added to 10 volumes hydrogen peroxide (3% H 0 100 g. The pH of the resulting solution is 3.8. This mixture is then applied to the hair and the temperature rises to 50 C. after 5 minutes. After a Wait of 15 minutes the hair is set in the customary manner.

It is observed that the hair set holds very well, the hair being lightened by 1 to 1 /2 tones, with a distinct golden copper glint. Moreover, the hair is lively and brilliant.

6 EXAMPLE 5 To prepare a composition which effects a tintinglightening of light chestnut hair, the two following mixtures are prepared:

G. A copolymer vinylpyrrolidone and vinyl acetate,

E735, sold by General Aniline 2 Absolute ethyl alcohol 40 Hydrogen peroxide 30 volumes (9% H 0 33 Water in sufficient quantity to make up F.M.C. crystal violet (crystal violet: C.I. basic violet 3) 0.02 Dimethylolethylene thiourea 100 When the novel composition of this invention is to be used, 100 g. of mixture (A) is added to 6.5 g. of mixture (B). The pH of the resulting composition is 3.6 and it is then applied to the hair. The temperature rises to 50 C. after 10 minutes, and the composition is allowed to remain in contact with the hair for a total of 20 minutes. The hair is then set in the usual Way and there is observed a distinct lightening of 1 to 1 /2 tones with a fine sheen. The hair is lively and exhibits a silky feel.

EXAMPLE 6 For moderate decoloration of chestnut colored hair, 1.6 g. dimethylolethylene thiourea are added, at the time of use, to the following mixture:

Ammonia oil 33 20 volumes H 0 (6% H 0 67 The ammonia oil is prepared as follows:

Nonyl phenol hydroxyethylene, with 4 moles ethylene oxide (Remcopal 334Gerland) g 30 Nonyl phenol hydroxyethylene, with 9 moles ethylene oxide (Remcopal 349--Gerland) g 20 Butyl glycol (Naphthachimie) g-- 15 Ammonia 21 B. cc 20 Water in sufiicient quantity to make up 100 g.

The pH of the resulting mixture is 10.1 and this composition is applied to the hair. The temperature rises to 50 C. after 5 minutes and it is allowed to remain in contact with the hair for 20 minutes. The hair is then Washed with Water and rinsed with an aqueous solution of lactic acid having a pH of 4. After drying the hair is set and it is found that the hair has a dark blond hue with a golden glint. Moreover, the hair is soft to the touch, and lively.

EXAMPLE 7 To effect a strong bleaching of chestnut hair, 0.6 g. dimethylol thiourea is added at the time of use to the following composition:

G. Potassium persulfate l0 Ammonium diphosphate 5 Anhydrous sodium metasili'cate 5 Hydrogen peroxide 20 volumes 100 The pH of the resulting composition is 10.2 and it is then applied to the hair. The temperature rises to 33-35 C., and the composition is thus allowed to act for a period of 45 to 60 minutes. The hair is then Washed and rinsed with an aqueous solution of lactic acid having a pH of 4. Thereafter the hair is dried and it is found to have a light golden blond color, and is lively and pleasant to the touch. The same effect can be attained by replacing the 0.6 g. dimethylol thiourea with 0.5 g. monomethylol thiourea or 0.7 g. dimethylolethylene thiourea.

7 EXAMPLE 8 For strong bleaching with tinting and a strengthening of chestnut colored hair, 0.7 g. dimethylolethylene thiourea is added, at the time of use, to a solution having the following composition:

Potassium persulfate g 10 Ammonium diphosphate g Anhydrous sodium metasilicate g 4.94 Acetoquinone violet 5 *RZ (F.M.C.) [C.I. dispersed violet 3] g 0.06 Hydrogen peroxide 20 volumes ml 100 The pH of the resulting composition is 10.2.

The composition is applied to the hair, the temperature rising rapidly to 33-35 C. The composition is then allowed to contact the hair for 45 to 60 minutes. Subsequently the hair is washed with water and rinsed with an aqueous solution of lactic acid having a pH of 4. After drying, it is found that the hair has a light golden blond coloration, with a faint glint. The general condition of the hair is excellent, lively and more brilliant. The same effect can be obtained by replacing, in the above example, the 0.7 g. dimethylolethylene thiourea with 0.5 g. monomethylol thiourea or with 0.6 g. dimethylol thiourea.

EXAMPLE 9 For strong bleaching and strengthening of chestnut hair, 0.2 g. dimethylolethylene thiourea is added to a solution obtained by dissolving 14 g. powder of the following composition in 100 ml. 20 volumes hydrogen peroxide (6% H 0 G. Sodium percarbonate 50 Ammonium diphosphate 36 Anhydrous sodium metasilicate 14 The solution has a pH of 9.6.

The composition is applied to the hair, the temperature rising to 3335 C. The composition is allowed to remain in contact with the hair for 45 to 60 minutes, after which the hair is then washed with water and rinsed with an aqueous solution of lactic acid having a pH of 4. Subsequently the hair is dried under a hood and has a light golden blond coloration. It is also lively and silky to the touch. Such a result could not have been obtained without the presence of the active methylol compound in the composition.

EXAMPLE 10 A weak decolorant composition is prepared by adding 0.8 g. methoxymethyl thiourea to 100 g. hydrogen peroxide, 20 volumes (6% H 0 at the same time of its use. The pH of the composition is 4.0 and is applied to dark blond hair. The composition is allowed to act for 20 minutes. After 3 to 6 minutes, the temperature reaches 5052 C. and the hair is rinsed and then set in the usual manner. There is a distinct lightening of the hair by 1 to 1 /2 tones and the thus treated hair is lively and brilliant.

EXAMPLE 11 The same conditions are employed as in Example 10, but the methoxymethyl thiourea is replaced by 1.1 g. dimorpholino-methylethylene thiourea. The pH of the resulting composition in this case is 5.8. After application of this composition to the hair and treatment as in EX- ample 10, there is a lightening of 1 to 1 /2 tones. The hair is also brilliant and lively, and the set holds very well.

EXAMPLE 12 To obtain decoloration with tinting and strengthening of light chestnut hair, a composition according to the present invention is prepared by adding, at the time of use, 0.8 g. dimorpholinomethyl thiourea to 100 g. hydrogen peroxide, 20 volumes (6% H 0 The pH of the resulting composition is 6 and it is applied to the hair which is light chestnut in color. The composition is allowed to act for about minutes. After 2 to 5 minutes the temperature reaches 4850 C. The hair is then rinsed and then set in the usual manner. There is a lightening by 1 to 1 /2 tones and the hair which has a coppery gold sheen is lively and brilliant and the set holds very well.

EXAMPLE 13 To obtain a composition which imparts a timing lightening to light chestnut colored hair, the following two mixtures are prepared:

G. Copolymer of vinylpyrrolidone and vinyl acetate 'E-735, K (1% ethanol) 50, sold commercially by General Aniline 2 Absolute ethyl alcohol 30 Hydrogen peroxide 30 volumes (9% H 0 Water in sufiicient quantity to make up 100 g.

Crystalline violet F.M.C. (Crystal violet 01. basic violet 3) 0.02 Dimorpholinomethyl thiourea 100 EXAMPLE 14 To effect moderate decoloration of dark chestnut hair. 3.3 g. dimorpholino methylethylene thiourea is added, at the time of use, to the following mixture:

G. Ammonia oil 33 Hydrogen peroxide 30 volumes (6% H 0 67 The ammonia oil corresponds in this case to the following preparation:

Nonylphenol hydroxyethylene with 4 moles ethylene oxide (Remocopal 334-Gerland) g 15 Nonylphenol hydroxyethylene with 9 moles ethylene oxide (Remcopal 349Gerland) g 15 20% ammonia cc 25 Water in sufiicient quantity to make up 100 g.

The pH of the resulting mixture is 9.85 and is applied to the hair, the temperature rising to C. after 10 minutes. The composition is allowed to act on the hair for 25 minutes. The hair is then Washed with water and rinsed with an aqueous solution of lactic acid having a pH of 4. After drying the hair is set and it is found that the hair has a dark blond hue with golden glint. Moreover, the hair is soft to the touch, brilliant and lively.

What is claimed is:

1. A cosmetic composition for bleaching human hair comprising an aqueous solution of an active compound of the formula wherein R and R are selected from the group consisting of hydrogen and -CH CH when joined together, R is selected from the group consisting of OH, OCH and and R is selected from the group consisting of hydrogen,

L/ and an oxidizing agent comprising an aqueous solution of hydrogen peroxide present in amounts of about 3-9 percent of said solution, said oxidizing agent being present in amounts of about 15-995 weight percent of said composition.

2. The cosmetic composition of claim 1 wherein said oxidizing agent also includes a per salt selected from the group consisting of sodium percarbonate, potassium persulfate and mixtures thereof, said per salt being present in amounts of about 5-10 percent by weight of said composition.

3. The cosmetic composition of claim 1 wherein said oxidizing agent also includes urea peroxide.

4. The composition of claim 1 wherein said active agent is selected from the group consisting of monomethylol thiourea, methoxymethyl thiourea, dimethylol thiourea, monomethylolethylene thiourea, dimethylolethylene thiourea, dimorpholinomethyl thiourea, monomorpholinomethyl thiourea and dimorpholinomethylethylene thiourea.

5. A process for the decoloration of human hair com- References Cited UNITED STATES PATENTS 3,193,464 7/1965 Edman et a1. 424-62 3,341,418 9/1967 Moses et a1 424-73 X 3,557,004 6/1971 Yolles 424 X 3,578,387 5/1971 Zviak et al 424-62 X FOREIGN PATENTS 443,567 2/ 1968 Switzerland 42471 ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner U.S. CL. X.R.

8-10, 10.1; 1327; 424-DIG. 3, 62, 70, 71

UNITED STATES PATENT OFFICE CERTIFECATE @EF CQRRECTEON Patent No. 3,7 3 Dated April 973 Giuliana Ghilardi, Gregoire Kalopissis, lnventol-(s) Henri Philippe de Beaulieu and Jean-Louis Abegg It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 5, change "R to --R Column 2, line 15, change --O-R to -O-R Column 9, line 2, change CH CH" to --CH OH-.

Signed and sealed this 19th day of February 19%..

(SEAL) Attest:

EDWARD M.F'LETCHER,JR.

MARSHALL DANN Attesting Officer Commissioner of Patents UNiTEn STATES PATENT @FHCE CERTH ECATE GK QURRECTWN Patent No. 3,7 3 Dated p i 10, 1973 Giuliana Ghilardi, Gregoire Kalopissis,- 4 lnventofls) Henri Philippe de Beaulieu and Jean-Louis Abegg It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 5, change "R to --R 7 Column 2, line 15, change "-O-R5-H to -0-R Column 9, line 2, change "CH CH" to --CH OH--.

Signed and sealed this 19th day of February 19714..

(SEAL) Attest:

EDWARD M.FLETCHER,JR.

Commissioner of Patents FORM PC1050 0(3) uscomm-nc conec; Y--\ 

